WO2021070550A1 - Méthode de production de pentafluorure de brome - Google Patents

Méthode de production de pentafluorure de brome Download PDF

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WO2021070550A1
WO2021070550A1 PCT/JP2020/034334 JP2020034334W WO2021070550A1 WO 2021070550 A1 WO2021070550 A1 WO 2021070550A1 JP 2020034334 W JP2020034334 W JP 2020034334W WO 2021070550 A1 WO2021070550 A1 WO 2021070550A1
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bromine
gas
pentafluoride
reaction
reactor
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PCT/JP2020/034334
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English (en)
Japanese (ja)
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一真 松井
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昭和電工株式会社
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Priority to KR1020227005169A priority Critical patent/KR20220035201A/ko
Priority to US17/610,187 priority patent/US20220219982A1/en
Priority to EP20874370.8A priority patent/EP4043392A4/fr
Priority to JP2021550535A priority patent/JPWO2021070550A1/ja
Priority to CN202080040439.0A priority patent/CN113905979A/zh
Publication of WO2021070550A1 publication Critical patent/WO2021070550A1/fr
Priority to IL290311A priority patent/IL290311A/en

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Definitions

  • the present invention relates to a method for producing bromine pentafluoride.
  • Bromine pentafluoride (BrF 5 ) generally reacts a bromine-containing compound, which is at least one of bromine gas (Br 2 ) and bromine trifluoride (BrF 3 ), with fluorine gas (F 2 ).
  • a bromine-containing compound which is at least one of bromine gas (Br 2 ) and bromine trifluoride (BrF 3 )
  • fluorine gas (F 2 ) fluorine gas
  • Patent Document 1 bromine gas or bromine trifluoride and fluorine gas are mixed in a reactor filled with nickel fluoride (NiF 2 ), and the molar ratio F / Br of fluorine atom to bromine atom is 5 or more.
  • a method for obtaining bromine pentafluoride by supplying and reacting with the above is disclosed.
  • An object of the present invention is to provide a method for producing bromine pentafluoride, which has a small amount of unreacted fluorine gas remaining and can produce high-purity bromine pentafluoride.
  • one aspect of the present invention is as follows [1] to [11].
  • a bromine-containing compound which is at least one of bromine gas and bromine trifluoride, is reacted with fluorine gas so that the molar ratio F / Br of fluorine atoms to bromine atoms is 3.0 or more and 4.7 or less.
  • a separation step for separating bromine pentafluoride and bromine trifluoride in the reaction mixture and A method for producing bromine pentafluoride.
  • an inert gas is supplied into the reactor together with the bromine-containing compound and the fluorine gas to carry out the reaction, and the supply amount of the inert gas is adjusted to the bromine-containing compound and the fluorine.
  • the gas component containing the bromine pentafluoride obtained in the cooling step is brought into contact with the adsorbent and mixed with the gas component containing the bromine pentafluoride.
  • the method for producing bromine pentafluoride according to [9] wherein the adsorbent is at least one selected from LiF, NaF, KF, RbF, CsF, MgF 2 , and CaF 2.
  • bromine pentafluoride According to the method for producing bromine pentafluoride according to the present invention, it is possible to produce high-purity bromine pentafluoride with a small amount of unreacted fluorine gas remaining.
  • the present embodiment shows an example of the present invention, and the present invention is not limited to the present embodiment.
  • various changes or improvements can be added to the present embodiment, and the modified or improved forms can also be included in the present invention.
  • the materials, dimensions, etc. exemplified in the present embodiment are examples, and the present invention is not limited thereto, and can be appropriately modified and carried out within the range in which the effects of the present invention are exhibited. Is.
  • the method for producing bromine pentafluoride of the present embodiment includes a reaction step and a separation step.
  • the reaction step is a step of reacting a bromine-containing compound which is at least one of bromine gas and bromine trifluoride with fluorine gas to obtain a reaction mixture containing bromine pentafluoride and bromine trifluoride.
  • the bromine-containing compound and fluorine gas are supplied into the reactor so that the molar ratio F / Br of the fluorine atom and the bromine atom is 3.0 or more and 4.7 or less, and the inside of the reactor is charged.
  • the reaction between the bromine-containing compound and fluorine gas is carried out in.
  • the separation step is a step of separating bromine pentafluoride and bromine trifluoride in the reaction mixture obtained in the reaction step.
  • the amount of fluorine gas used is less than the reaction equivalent, so that unreacted fluorine gas does not remain at all, or even if it remains, it is a small amount. Therefore, it is possible to reduce or simplify the process of treating the remaining fluorine gas by a method such as recovery or abatement. Further, since the amount of fluorine gas used is small, the amount of fluorine gas used can be suppressed, and the amount of fluorine gas discharged from the reactor can be suppressed.
  • the method for producing bromine pentafluoride of the present embodiment includes a separation step of separating bromine pentafluoride and bromine trifluoride, a high-purity (for example, 90% or more purity) pentafluoride is used. It is possible to produce bromide. That is, in the separation step, the components of the reaction mixture other than fluorine gas and bromine pentafluoride can be efficiently removed, so that the amount of fluorine gas remaining in the reaction mixture is small, and the bromine pentafluoride of the present embodiment is produced.
  • the method is advantageous for obtaining high purity bromine pentafluoride.
  • the obtained bromine pentafluoride can be used as an etching gas, a cleaning gas, a fluorinating agent and the like in the fields of organic synthesis, inorganic synthesis, nuclear power, semiconductor manufacturing and the like.
  • bromine pentafluoride when the bromine-containing compound is bromine gas (Br 2 ), the raw material compounds are fluorine gas and bromine gas. By reacting with and as shown in the chemical reaction formula (1) shown below, bromine pentafluoride, which is the target product, is produced. 5F 2 + Br 2 ⁇ 2BrF 5 ... (1)
  • bromine-containing compound is bromine gas (Br 2 )
  • the raw material compounds, fluorine gas and bromine gas react in two steps as shown in the following chemical reaction formulas (2) and (3).
  • bromine pentafluoride which is the target product
  • the target compound is generated by the reaction between the fluorine gas as the raw material compound and the bromine trifluoride gas as shown in the chemical reaction formula (3) shown below.
  • the product, bromine pentafluoride is produced.
  • the method of supplying the fluorine gas to the reactor in the method for producing bromine pentafluoride of the present embodiment is not particularly limited, but for example, the fluorine gas is compressed.
  • the temperatures of the fluorine gas and the mixed gas when supplied to the reactor are not particularly limited as long as the gas supply mechanism can operate.
  • the gas supply mechanism is not particularly limited as long as it has a mechanism that can control the flow rate of gas, but from the viewpoint of availability, a mass flow controller, a flow meter, or the like may be used. preferable.
  • a mass flow controller is used as an example of the gas supply mechanism will be shown.
  • the method for supplying the bromine-containing compound (for example, bromine gas, bromine trifluoride) in the method for producing bromine pentafluoride of the present embodiment is not particularly limited, but for example, a mass flow controller is connected. Examples thereof include a method in which the bromine-containing compound is heated and vaporized in the vaporizer, and the gas of the bromine-containing compound is supplied to the reactor while controlling the flow rate with the mass flow controller.
  • a method of vaporizing the bromine-containing compound using an inert gas can also be used. That is, a mass flow controller is connected to a container filled with an inert gas by compression, and the inert gas is supplied to the vaporizer containing the bromine-containing compound while controlling the flow rate with the mass flow controller, and the inert gas is contained in the vaporizer.
  • a mass flow controller is connected to a container filled with an inert gas by compression, and the inert gas is supplied to the vaporizer containing the bromine-containing compound while controlling the flow rate with the mass flow controller, and the inert gas is contained in the vaporizer.
  • This is a method in which a bromine compound is vaporized and a mixed gas of a bromine-containing compound and an inert gas having a controlled flow rate is supplied to the reactor.
  • the inert gas may be blown into the liquid bromine-containing compound, or the inert gas may be supplied to the gas phase portion in the vaporizer.
  • the temperature inside the vaporizer when the bromine-containing compound is vaporized and supplied to the reactor can be appropriately changed depending on the supply rate of the bromine-containing compound to the reactor.
  • the temperature inside the vaporizer is preferably 10 ° C. or higher and 60 ° C. or lower, and when the bromine-containing compound is bromine trifluoride, the temperature inside the vaporizer is The temperature is preferably 30 ° C. or higher and 130 ° C. or lower. If the temperature inside the vaporizer is within the above temperature range, the vapor pressure of the bromine-containing compound becomes sufficiently high, so that the productivity of bromine pentafluoride is excellent, and the vaporizer using the bromine-containing compound. , Piping, reactor, etc. are less likely to corrode.
  • the molar ratio F / Br of fluorine atom to bromine atom is 3.0 or more and 4.7 or less. As described above, it is necessary to supply the bromine-containing compound and the fluorine gas into the reactor to carry out the reaction between the bromine-containing compound and the fluorine gas.
  • the molar ratio F / Br of the fluorine atom to the bromine atom is 3.0 or more and 4.7 or less, the amount of unreacted bromine-containing compound is reduced, so that the amount of unreacted fluorine gas is reduced and the amount of unreacted fluorine gas is reduced.
  • the molar ratio F / Br of the fluorine atom and the bromine atom is 3.3 or more and 4.5 or less.
  • the fluorine gas in the reaction can be 40% or more. The time that the gas of the raw material compound stays in the reactor will be described in detail later.
  • the diluting gas for diluting the raw material compound is reacted with the gas of the bromine-containing compound which is the raw material compound and the fluorine gas. It may be supplied into the vessel to carry out the reaction. That is, the reaction between the bromine-containing compound and the fluorine gas may be carried out in a state where the diluted gas is mixed with the bromine-containing compound gas and the fluorine gas and diluted.
  • the diluting gas a bromine-containing compound and a fluorine gas as a raw material compound, bromine pentafluoride as a target product, and an inert gas that does not react with bromine trifluoride as an intermediate or a by-product may be used.
  • the type of the inert gas is not particularly limited, and examples thereof include nitrogen gas, argon, and helium. Among these inert gases, nitrogen gas is preferable as the diluting gas from the viewpoint of easy availability and low cost.
  • the amount of the diluting gas supplied into the reactor together with the raw material compound is not particularly limited, but is 30 volumes of the total volume of the gas of the bromine-containing compound in the reactor, the fluorine gas, and the diluting gas. % Or more, more preferably 50% by volume or more. When it is set to 30% by volume or more, the risk of local reaction or runaway reaction can be sufficiently reduced, so that bromine pentafluoride can be produced more safely.
  • the amount of the dilution gas supplied into the reactor together with the raw material compound is the gas of the bromine-containing compound in the reactor, the fluorine gas and the dilution gas.
  • the total volume of the gas is preferably 99% by volume or less, and more preferably 90% by volume or less.
  • the method for carrying out the reaction between the bromine-containing compound and the fluorine gas at a temperature of 100 ° C. or higher and 400 ° C. or lower is not particularly limited, but for example, the temperature inside the reactor is adjusted to 100 ° C. or higher and 400 ° C. or lower. Then, a method of supplying the gas of the bromine-containing compound and the fluorine gas into the reactor can be mentioned.
  • the method for adjusting the temperature inside the reactor to 100 ° C. or higher and 400 ° C. or lower is not particularly limited, but for example, the reactor is heated by a heating means such as an electric heater or steam, or in some cases.
  • a heating means such as an electric heater or steam, or in some cases.
  • a method of adjusting the temperature inside the reactor by cooling with a jacket into which a refrigerant has flowed in can be mentioned.
  • the reactor When the reaction between the bromine-containing compound and fluorine gas is carried out with the catalyst placed in the reactor, the reactor is heated with the catalyst placed in the reactor to obtain the desired reactor and catalyst. After adjusting to the temperature, it is advisable to supply the bromine-containing compound gas and the fluorine gas into the reactor. The higher the temperature of the catalyst, the higher the conversion rate of fluorine gas.
  • the pressure in the reactor during the reaction is the method for separating and recovering the bromine-containing compound and the target product, pentafluoride. It can be arbitrarily set according to the method for recovering bromine.
  • the reaction between the bromine-containing compound and the fluorine gas is preferably carried out under a pressure of 0.05 MPa or more and 0.5 MPa or less, and more preferably 0.1 MPa or more and 0.5 MPa or less. , It is more preferable to carry out under a pressure of 0.1 MPa or more and 0.2 MPa or less.
  • the pressure in the present invention means an absolute pressure unless otherwise specified.
  • the reaction temperature is such that the reverse reaction of bromine pentafluoride decomposing into bromine trifluoride and fluorine gas is not remarkable, the conversion rate of fluorine gas increases as the residence time increases.
  • the residence time is preferably 5 seconds or more, and then the fluorine gas
  • the conversion rate can be 40% or more.
  • a catalyst is arranged in a reactor and a raw material such as a bromine-containing compound and fluorine gas is used during the reaction.
  • the reaction between the bromine-containing compound and fluorine gas may be carried out in coexistence with the compound.
  • the catalyst preferably has low reactivity with a bromine-containing compound, fluorine gas, and bromine pentafluoride, and examples of the compound used as a catalyst include at least one of a metal oxide and a metal fluoride.
  • This metal is at least one of the metals belonging to the 3rd and 4th periodic elements of the periodic table.
  • metal fluorides include aluminum fluoride (AlF 3 ), calcium fluoride (CaF 2 ), iron fluoride (III) (FeF 3 ), cobalt fluoride (II) (CoF 2 ), and foot.
  • Nickel (II) fluoride (NiF 2 ), copper (I) fluoride (CuF), potassium fluoride (KF), magnesium fluoride (MgF 2 ), sodium fluoride (NaF) and the like can be mentioned, and metal oxides can be mentioned.
  • cobalt oxide (II) (CoO) is Can be mentioned.
  • AlF 3 , FeF 3 , CoF 2 , NiF 2 , and ⁇ -Al 2 O 3 are more preferable in consideration of low reactivity with bromine-containing compounds, fluorine gas, and bromine pentafluoride and availability.
  • the catalyst does not contain water.
  • fluorine gas, bromine gas, bromine trifluoride, and bromine pentafluoride react with water during the production of bromine pentafluoride to form hydrogen fluoride (HF) and hydrogen bromide (hydrogen bromide).
  • HF hydrogen fluoride
  • hydrogen bromide hydrogen bromide
  • HBr hydrogen bromide
  • the shape of the catalyst is particularly limited as long as the fluorine gas, bromine gas, and bromine trifluoride gas circulating in the reactor can be efficiently contacted and these gases are not blocked in the reactor. Not done.
  • fluorine gas chlorine trifluoride gas (ClF 3 ), iodine heptafluoride gas (IF 7 ), or bromine pentafluoride gas is brought into contact with a metal porous body or metal mesh at a high temperature.
  • the metal surface obtained by fluorinating the metal surface to generate metal fluoride can be used as a catalyst.
  • a commercially available metal fluoride or metal oxide powder molded into pellets, or a commercially available metal fluoride or metal oxide molded product can be used as it is.
  • the shape of the catalyst is preferably porous or mesh.
  • a porous body having a pore diameter of 0.3 mm or more and 3.2 mm or less and a specific surface area of 500 m 2 / m 3 or more and 10000 m 2 / m 3 or less and a wire diameter of 0.04 mm or more and 0.
  • a mesh having a mesh size of 8 mm or less and an opening of 0.04 mm or more and 0.98 mm or less is more preferable.
  • the reactor used in the method for producing bromine pentafluoride of the present embodiment has a structure capable of allowing the gas of the bromine-containing compound, which is a raw material compound, and the fluorine gas to come into contact with the catalyst.
  • a flow reactor or a batch reactor can be used.
  • the shape of the reactor may be a tube type or a tank type, the tube type may be a single tube type or a multi-tube type, and the catalyst filling form may be a fluidized bed or a fixed bed.
  • the shape of the reactor is preferably a single tube type or a multi-tube type, and the catalyst filling form is preferably a fixed bed.
  • the bromine-containing compound gas and the fluorine gas may be mixed in advance and introduced into the batch reactor, or the bromine-containing compound gas and the fluorine gas may be separately contained in the batch reactor. May be supplied to.
  • the order in which these raw material compounds are supplied into the reactor is not particularly limited, and the bromine-containing compound gas and the fluorine gas are reacted at the same time. It may be supplied into the reactor or sequentially supplied into the reactor.
  • a flow-type tubular reactor as the reactor.
  • the shape of the flow-type tubular reactor is not particularly limited as long as it can circulate a bromine-containing compound gas, fluorine gas, etc., but a catalyst such as NiF 2 is arranged in the reactor. In some cases, it is preferable to have a cavity so that the catalyst can be accommodated and the gas can flow in the state of accommodating the catalyst.
  • the inner surface of the tubular reactor is rough, resistance occurs when the gas flows through the tubular reactor, and the gas Retention, increased pressure loss, abnormal heat generation due to local reaction, etc. may occur, making it difficult to control the reaction. Therefore, it is preferable that the inner surface of the tubular reactor is smooth. Specifically, it is preferable to use a brightly annealed tube having a smooth inner surface as a tubular reactor, which is manufactured by a method having a step of heating and quenching in an non-oxidizing atmosphere such as an inert gas or vacuum.
  • the reactor used in the method for producing bromine pentafluoride of the present embodiment needs to be made of a material having corrosion resistance to fluorine gas or a bromine-containing compound gas.
  • metals such as nickel, nickel-based alloys, aluminum, stainless steel, and platinum, and ceramics such as alumina can be exemplified.
  • the nickel-based alloy include Inconel (registered trademark), Hastelloy (registered trademark), Monel (registered trademark) and the like.
  • the temperature inside the reactor is 150 ° C. or higher, it is preferable to select nickel, nickel-based alloy, platinum, or alumina, which are particularly excellent in corrosion resistance, among the above materials, and they are easily available and relatively inexpensive. Nickel and nickel-based alloys are particularly preferable.
  • the metal oxide and metal fluoride used as the catalyst can also be used as the material of the reactor.
  • nickel tube As the reactor used in the method for producing bromine pentafluoride of the present embodiment, it is preferable to use a brightly burned nickel tube.
  • nickel is a brightly baked blunt tube. Since the surface is smooth, the risk of the above-mentioned abnormal reaction between the gas and the metal residue and damage to the reactor can be minimized.
  • the inner surface of the reactor is fluorinated by fluorine gas, bromine trifluoride gas, and bromine pentafluoride gas, and NiF 2 Can change to.
  • NiF 2 can be used as a catalyst in the method for producing bromine pentafluoride of the present embodiment, it does not matter if the inner surface of the reactor is changed to NiF 2.
  • the inner surface of the reactor is fluorinated by the reaction between the metal and fluorine gas, bromine trifluoride gas, and bromine pentafluoride gas.
  • nickel-based alloys having a nickel content of 50% by mass or more and containing iron, copper, chromium, molybdenum, etc. (for example, Inconel (registered trademark) and Hastelloy (registered trademark)) are used as materials for brightly burned tubes. , Monel®) and NiF 2 can be used.
  • the method for producing bromine pentafluoride of the present embodiment has a separation step, and separates bromine pentafluoride and bromine trifluoride in the reaction mixture obtained in the reaction step. Separate in the process.
  • the separation step may include a cooling step of cooling the reaction mixture and separating it into a gas component containing bromine pentafluoride and a liquid solid component containing bromine trifluoride.
  • a cooling collection container For cooling the reaction mixture, for example, a cooling collection container can be used.
  • a cooling collection vessel When the reaction mixture obtained in the reaction step is supplied to a cooling collection vessel and cooled to a temperature at which bromine trifluoride is solidified or liquefied and bromine pentafluoride is not solidified or liquefied, bromine trifluoride and bromine pentafluoride are cooled. Can be separated. For example, when cooled to 0 ° C., most of the bromine trifluoride becomes a solid and is collected in a cold collection container (hereinafter, may be referred to as a “cool collection container for collecting bromine trifluoride”). Although collected, most of the bromine pentafluoride passes through the cooling collection vessel as a gas.
  • bromine trifluoride becomes a solid in the cold collection container, but some liquid or gaseous bromine trifluoride also exists and may pass through the cold collection container. It is preferable to further perform an operation of separating bromine trifluoride from the gas that has passed through. This operation will be described in detail in Section [12].
  • a diluting gas such as nitrogen gas
  • the diluting gas is accompanied by the reaction mixture, so that a part of bromine pentafluoride is collected as a liquid in a cooling collection container.
  • most of the bromine pentafluoride easily passes through the cold collection container as a gas.
  • the cooling temperature of the reaction mixture in the cooling collection vessel is preferably in the range of ⁇ 20 ° C. or higher and 30 ° C. or lower, and more preferably in the range of ⁇ 10 ° C. or higher and 20 ° C. or lower.
  • bromine trifluoride can be collected with high efficiency, and since the amount of bromine pentafluoride collected is small, the separation efficiency of bromine pentafluoride and bromine trifluoride is high. .. If collection is performed at a temperature below the melting point of bromine trifluoride, there is a concern that bromine trifluoride will solidify in the pipe connected to the cooling collection container and the pipe will be clogged.
  • the pressure inside the cooling collection container is preferably 0.05 MPa or more and 0.5 MPa or less, and more preferably 0.1 MPa or more and 0.3 MPa or less.
  • the bromine pentafluoride that has passed through the cold collection container is supplied to another cold collection container (hereinafter, may be referred to as "cool collection container for collecting bromine pentafluoride"), and the five.
  • cool collection container for collecting bromine pentafluoride When cooled to a temperature at which bromine fluoride solidifies or liquefies, bromine pentafluoride can be collected in another cooling collection vessel.
  • the cooling temperature in the cooling collection container for collecting bromine pentafluoride is not particularly limited as long as it is below the boiling point of bromine pentafluoride. However, in order to improve the collection efficiency of bromine pentafluoride, it is preferable to cool the bromine pentafluoride to a temperature at which the vapor pressure becomes sufficiently low.
  • the cooling temperature in the cooling collection container for collecting bromine pentafluoride is preferably in the range of ⁇ 100 ° C. or higher and 0 ° C. or lower, and more preferably in the range of ⁇ 80 ° C. or higher and ⁇ 20 ° C. or lower.
  • bromine pentafluoride solidifies in the pipe connected to the cooling collection container for collecting bromine pentafluoride, and the pipe is clogged. Although there is a concern that this may occur, if a diluent gas is used in the reaction process and the reaction mixture is accompanied by the diluent gas, blockage of the pipe due to solidification of bromine pentafluoride can be suppressed.
  • the pressure inside the cooling collection container here is preferably 0.05 MPa or more and 0.5 MPa or less, and more preferably 0.1 MPa or more and 0.3 MPa or less.
  • the cold collection container for collecting bromine trifluoride and the cold collection container for collecting bromine pentafluoride are for fluorine gas, bromine gas, bromine trifluoride gas, and bromine pentafluoride gas. It needs to be made of a material that is hard to react and has corrosion resistance. Specifically, metals such as nickel, nickel-based alloys, aluminum, stainless steel, and platinum, and ceramics such as alumina can be exemplified. Specific examples of the nickel-based alloy include Inconel (registered trademark), Hastelloy (registered trademark), Monel (registered trademark) and the like. Further, the inner surface of the cooling collection container made of the metal that comes into contact with fluorine gas or the like may be fluorinated. Of these, Monel®, aluminum, alumina and stainless steel, which are easily available and relatively inexpensive, are particularly preferred.
  • the method for producing bromine pentafluoride of the present embodiment has a separation step, and the bromine pentafluoride and the bromine trifluoride in the reaction mixture obtained in the reaction step are used. Is separated in the separation step.
  • the separation step includes a cooling step of cooling the reaction mixture and separating it into a gas component containing bromine pentafluoride and a liquid solid component containing bromine pentafluoride, and the pentafluoride obtained by the cooling step.
  • an adsorption tower can be used for the adsorption of bromine trifluoride.
  • the type of adsorbent to be filled in the adsorption tower is not particularly limited as long as it is difficult to adsorb bromine pentafluoride and can adsorb bromine trifluoride, but it is not particularly limited as long as it can adsorb bromine pentafluoride.
  • At least one fluoride of metals belonging to Group 2 elements can be used. As shown in the chemical reaction formula (4), the fluorides of these metals react with bromine trifluoride to form salts, but do not react with bromine pentafluoride to form salts. Selective separation of bromide can be performed.
  • M represents a metal and x represents 1 or 2.
  • the adsorption temperature of bromine trifluoride that is, the temperature inside the adsorption tower when the gas component containing bromine pentafluoride obtained in the cooling step is brought into contact with the adsorbent in the adsorption tower is 0 ° C. or higher and 100 ° C. or lower.
  • the range of 20 ° C. or higher and 70 ° C. or lower is more preferable. Within this temperature range, solidification of bromine trifluoride and liquefaction of bromine pentafluoride are unlikely to occur, so that the adsorption tower and the pipes connected to the adsorption tower are less likely to be clogged. Since desorption of bromine trifluoride is unlikely to occur, bromine trifluoride can be sufficiently separated.
  • the pressure inside the adsorption tower is preferably 0.05 MPa or more and 0.5 MPa or less, and more preferably 0.1 MPa or more and 0.3 MPa or less.
  • the adsorption tower needs to be made of a material that does not easily react with fluorine gas, bromine gas, trifluoride bromine gas, and pentafluoride bromine gas and has corrosion resistance.
  • metals such as nickel, nickel-based alloys, aluminum, stainless steel, and platinum, and ceramics such as alumina can be exemplified.
  • the nickel-based alloy include Inconel (registered trademark), Hastelloy (registered trademark), Monel (registered trademark) and the like.
  • the inner surface of the adsorption tower made of the metal that comes into contact with fluorine gas or the like may be fluorinated.
  • Example of a bromine pentafluoride production apparatus The method for producing bromine pentafluoride according to the present embodiment can be carried out in the bromine pentafluoride production apparatus shown in FIG.
  • the bromine pentafluoride production apparatus shown in FIG. 1 supplies a reactor 1 that reacts a gas of a bromine-containing compound, which is at least one of bromine and bromine trifluoride, with a fluorine gas, and a fluorine gas to the reactor 1.
  • a fluorine gas supply device 2 a mass flow controller 11 that controls the flow rate of the fluorine gas supplied from the fluorine gas supply device 2 to the reactor 1, an inert gas supply device 3 that supplies the inert gas to the reactor 1, and the like.
  • It houses a mass flow controller 12 that controls the flow rate of the inert gas supplied from the inert gas supply device 3 to the reactor 1 and a bromine-containing compound 6 that is at least one of liquid bromine and liquid trifluoride bromine. It also includes a vaporizer 4 that vaporizes the liquid bromine-containing compound 6 and supplies it to the reactor 1.
  • a metal (not shown) as a catalyst is arranged in the reactor 1. Further, the reactor 1 is provided with a heating device (not shown) such as an electric furnace, and the temperature inside the reactor 1 can be controlled to an arbitrary temperature.
  • the vaporizer 4 includes an inert gas supply device 5 that blows an inert gas into the liquid bromine-containing compound 6 in the vaporizer 4, and a flow rate of the inert gas supplied from the inert gas supply device 5 to the vaporizer 4.
  • a mass flow controller 14 for controlling the above and a heating device 13 for heating the liquid bromine-containing compound 6 in the vaporizer 4 are provided.
  • the bromine pentafluoride production apparatus shown in FIG. 1 cools a pressure gauge 15 for measuring the pressure in the reactor 1 and a reaction mixture containing bromine pentafluoride and bromine trifluoride, and bromine trifluoride.
  • First cold collection container 7 that separates bromine pentafluoride and bromine trifluoride by passing bromine pentafluoride through the above "Cold collection for collecting bromine trifluoride" (Corresponding to a container), an adsorption tower 8 filled with metal fluoride as an adsorbent, and a second cooling collection container 9 (which cools and collects bromine pentafluoride that has passed through the adsorption tower 8). It corresponds to the above-mentioned "cooled collection container for collecting bromine pentafluoride").
  • the first cooling collection container 7 is provided with a cooling tank 19, and the temperature inside the first cooling collection container 7 can be controlled by the cooling tank 19.
  • the second cooling collection container 9 is provided with a cooling tank 20, and the temperature inside the second cooling collection container 9 can be controlled by the cooling tank 20.
  • the reactor 1, the first cooling collection container 7, the adsorption tower 8, and the second cooling collection container 9 are arranged in series in the order described in this description, and are connected to each other by a pipe.
  • a pressure regulating valve 16, a Fourier transform infrared spectrophotometer 17, and an ultraviolet-visible spectrophotometer 18 are installed in the pipe connecting the reactor 1 and the first cooling collection vessel 7, and the pressure regulating valve 16
  • the Fourier transform infrared spectrophotometer 17 and the ultraviolet-visible spectrophotometer 18 are arranged in series from the reactor 1 side in this description order.
  • the liquid bromine-containing compound 6 in the vaporizer 4 is heated by the heating device 13 to vaporize the bromine-containing compound 6.
  • the liquid bromine-containing compound 6 and the gas of the bromine-containing compound 6 are present in the vaporizer 4.
  • the liquid bromine-containing compound 6 in the vaporizer 4 is blown with the inert gas from the inert gas supply device 5 while controlling the flow rate by the mass flow controller 14. By blowing the inert gas, the gas of the bromine-containing compound 6 is supplied from the vaporizer 4 to the reactor 1 while being diluted with the inert gas.
  • the fluorine gas is supplied from the fluorine gas supply device 2 to the reactor 1, and the flow rate is controlled by the mass flow controller 12 while being inactive from the inert gas supply device 3 to the reactor 1. Supply gas.
  • the concentration of the fluorine gas supplied to the reactor 1 can be controlled by the mass flow controllers 11 and 12.
  • the fluorine gas having a concentration of 100% can be supplied to the reactor 1. Further, if both the fluorine gas and the inert gas are supplied, the fluorine gas diluted to an arbitrary concentration with the inert gas can be supplied to the reactor 1.
  • the fluorine gas diluted to x% by volume with the inert gas will be referred to as "x% by volume fluorine gas".
  • x% by volume fluorine gas a fluorine gas diluted to 20% by volume with an inert gas is "20% by volume fluorine gas”
  • a fluorine gas diluted to 50% by volume with an inert gas is "50% by volume fluorine gas”
  • an inert gas is used.
  • the undiluted fluorine gas is described as "100% by volume fluorine gas”.
  • a bromine-containing compound gas and a fluorine gas are supplied to the reactor 1 to react the bromine-containing compound gas with the fluorine gas, and the molar ratio F / Br of the fluorine atom to the bromine atom is 3.0 or more and 4.7.
  • the reaction is carried out by supplying the gas of the bromine-containing compound and the fluorine gas as follows.
  • the pressure in the reactor 1 is measured by the pressure gauge 15.
  • a gaseous reaction mixture containing bromine pentafluoride and bromine trifluoride is obtained.
  • reaction mixture containing bromine pentafluoride, bromine trifluoride and an inert gas can be obtained.
  • the reaction mixture may contain unreacted fluorine gas, bromine gas, and bromine monofluoride (BrF), which is a by-product.
  • the obtained reaction mixture is sent to the Fourier transform infrared spectrophotometer 17 and the ultraviolet-visible spectrophotometer 18 while adjusting the pressure to about 0.1 to 0.2 MPa by the pressure regulating valve 16, and the Fourier transform infrared spectrophotometer is analyzed.
  • the mixture is sent to the first cold collection container 7. Since the temperature inside the first cooling collection vessel 7 is controlled to a predetermined temperature by the cooling tank 19, the reaction mixture is a liquid solid containing a gas component containing bromine pentafluoride and bromine trifluoride. Separated into components.
  • the bromine trifluoride in the reaction mixture is solidified and collected in the first cooling collection vessel 7.
  • Reference numeral 21 in FIG. 1 indicates solidified bromine trifluoride.
  • the reaction mixture contains unreacted bromine gas
  • the unreacted bromine gas is also solidified and collected in the first cooling collection container 7.
  • some of the bromine pentafluoride in the reaction mixture is liquefied and collected, most of it is gaseous, so that the gaseous bromine pentafluoride, unreacted fluorine gas and inert gas are present.
  • the mixed gas containing at least one of the gases is discharged from the first cooling collection container 7 and sent to the adsorption tower 8.
  • bromine trifluoride is mixed in the mixed gas that has passed through the first cooling collection container 7, and the bromine trifluoride forms a complex salt with the metal fluoride filled in the adsorption tower 8. Therefore, bromine trifluoride is selectively adsorbed and separated from the mixed gas by the adsorption tower 8. Therefore, the mixed gas that has passed through the adsorption tower 8 contains almost no bromine trifluoride.
  • the mixed gas containing bromine pentafluoride that has passed through the adsorption tower 8 is supplied to the second cooling collection container 9. Since the temperature inside the second cooling collection container 9 is controlled to a predetermined temperature by the cooling tank 20, bromine pentafluoride in the mixed gas is solidified or liquefied and collected.
  • Reference numeral 22 in FIG. 1 indicates solidified or liquefied bromine pentafluoride.
  • the bromine pentafluoride obtained here has a high purity of, for example, 90% or more.
  • At least one of the unreacted fluorine gas and the inert gas in the mixed gas is not collected in the second cooling collection container 9, and is discharged from the bromine pentafluoride production apparatus.
  • the bromine pentafluoride production apparatus of FIG. 2 which is a modification of the bromine pentafluoride production apparatus of FIG. 1, does not have an adsorption tower 8, and has a first cold collection container 7 and a second cold collection container 7.
  • the collection container 9 is directly connected by a pipe. Even when the bromine pentafluoride production apparatus of FIG. 2 having such a structure is used, bromine pentafluoride can be produced in the same manner as the bromine pentafluoride production apparatus of FIG.
  • the redox titration was carried out when 50% by volume of fluorine gas was passed through the brightly quenched tube for 3 hours, thereby confirming the completion of the reaction. Then, ion chromatography and inductively coupled plasma emission spectroscopic analysis were performed under the following equipment and conditions, and it was confirmed that NiF 2 was produced.
  • DIONEX ICS-2000 manufactured by Nippon Dionex Corporation -Eluent: Potassium hydroxide aqueous solution (gradient elution with a concentration of 4-40 mM) ⁇
  • Detector Electrical conductivity detector
  • Catalyst Preparation Example 3 The catalyst except that the nickel porous body is changed to a cobalt porous body with a purity of 99% (Nirako Co., Ltd., pore diameter 2.0 mm, specific surface area 6200 m 2 / m 3 , mass 29.5 g (0.5 mol)).
  • the catalyst (porous material made of CoF 2 ) was prepared and analyzed in the same manner as in Preparation Example 1.
  • Catalyst Preparation Example 4 Except for changing the nickel porous body to a 99% pure aluminum porous body (manufactured by Taisei Kogyo Co., Ltd., pore diameter 0.5 mm, specific surface area 7000 m 2 / m 3 , mass 27.9 g (0.5 mol)) , Preparation of catalyst The catalyst ( porous material made of AlF 3 ) was prepared and analyzed in the same manner as in Example 1.
  • Example 1 Bromine pentafluoride was produced using an apparatus substantially similar to the apparatus for producing bromine pentafluoride shown in FIG. Preparation of catalyst The bright quenching tube (reactor) provided with 48 g of the catalyst (porous body made of NiF 2 ) prepared in Example 1 was heated in an electric furnace, and the temperature inside the bright quenching tube (that is, the reaction temperature) was set to 280 ° C. Therefore, the temperature of the catalyst is also 280 ° C.
  • a vaporizer containing liquid bromine trifluoride as a bromine-containing compound is heated to 90 ° C., and then nitrogen gas is blown into the liquid bromine trifluoride to obtain bromine trifluoride gas. And supplied to the brightly baked blunt tube.
  • the flow rate of the nitrogen gas blown into the liquid bromine trifluoride was set to 300 sccm in terms of 101 kPa at 0 ° C., and the flow rate of the bromine trifluoride gas supplied to the bright quenching tube was set to 102 sccm.
  • the gas of the raw material compound was circulated in a brightly baked tube for 1 hour, and the reaction of obtaining bromine pentafluoride from fluorine gas and bromine trifluoride was continuously carried out. Then, Fourier transform infrared spectroscopic analysis and ultraviolet-visible spectroscopic analysis are performed on the gaseous reaction mixture discharged from the brightly quenched tube to obtain the composition of the reaction mixture (fluorine gas, bromine trifluoride, bromine pentafluoride, etc.). Concentration) was measured. At this time, assuming that the amount of nitrogen gas did not change, the composition of the reaction mixture and the conversion rate of fluorine gas were calculated.
  • the Fourier transform infrared spectroscopic analysis was performed using a Fourier transform infrared spectrophotometer Nicolet iS5 manufactured by Thermo Fisher Scientific, and the concentrations of bromine trifluoride and bromine pentafluoride were measured by the analysis.
  • the ultraviolet-visible spectrophotometric analysis was performed using an ultraviolet-visible spectrophotometer U-2900 manufactured by Hitachi High-Tech Science Co., Ltd., and the concentrations of bromine gas and fluorine gas were measured by the analysis.
  • Table 1 shows the reaction conditions, the gas composition of the raw material compound, the composition of the reaction mixture, and the conversion rate of fluorine gas.
  • the molar ratio F / Br of fluorine atoms to bromine atoms in the raw material compound is calculated by substituting the concentrations (volume%) of fluorine gas, bromine gas, and bromine trifluoride gas in the raw material compound into the following formula. be able to.
  • F / Br [3 x concentration of bromine trifluoride gas (volume%) + 2 x concentration of fluorine gas (volume%)] / [concentration of bromine trifluoride gas (volume%) + 2 x concentration of bromine gas (volume) %)]
  • the conversion rate (yield) of the fluorine gas is calculated by substituting the concentration of the fluorine gas in the gas of the raw material compound (volume%) and the concentration of the fluorine gas in the reaction mixture (volume%) into the following formula. can do.
  • Conversion rate (%) [Concentration of fluorine gas in gas of raw material compound (volume%)-Concentration of fluorine gas in reaction mixture (volume%)] / Concentration of fluorine gas in gas of raw material compound (volume%)
  • the gaseous reaction mixture discharged from the bright quenching tube was supplied to a first stainless steel cooling collection container (capacity: 500 mL) cooled to 0 ° C. under the condition of a pressure of 0.1 MPa to cool it. Bromine trifluoride was collected. The composition of the collected material collected in the first cooled collection container was measured by Fourier transform infrared spectroscopy and ultraviolet-visible spectroscopy. The results are shown in Table 2.
  • a stainless steel tube (inner diameter 12.7 mm) filled with sodium fluoride (purity 99%, mass 30 g (0.7 mol)) as an adsorbent for the gaseous reaction mixture that passed through the first cooling collection container. , 100 mm in length), and bromine trifluoride in the reaction mixture was adsorbed on an adsorbent under the condition of a temperature of 35 ° C.
  • the gaseous reaction mixture passed through the stainless steel tube was supplied to a second stainless steel cooling collection container (capacity: 500 mL) cooled to ⁇ 80 ° C. and cooled to collect bromine pentafluoride. ..
  • the composition of the collected material collected in the second cooled collection container was measured by Fourier transform infrared spectroscopy and ultraviolet-visible spectroscopy. The results are shown in Table 2.
  • the reaction and analysis were carried out in the same manner as in Example 1 except for a certain point. The results are shown in Tables 1 and 2.
  • Example 3 The reaction and analysis were carried out in the same manner as in Example 1 except that the reaction temperature (catalyst temperature) was 150 ° C. The results are shown in Tables 1 and 2.
  • Example 4 The reaction and analysis were carried out in the same manner as in Example 1 except that the reaction temperature was 150 ° C. and the reaction pressure (pressure in the brightly quenched tube) was 0.2 MPa. The results are shown in Tables 1 and 2.
  • Example 5 The reaction and analysis were carried out in the same manner as in Example 2 except that the reaction temperature was 120 ° C. The results are shown in Tables 1 and 2.
  • the reaction and analysis were carried out in the same manner as in Example 1 except that the value was 0.
  • the results are shown in Tables 1 and 2.
  • Example 7 The reaction and analysis were carried out in the same manner as in Example 1 except that the catalyst was changed to that prepared in Preparation Example 2 of the catalyst ( porous material made of FeF 3). The results are shown in Tables 1 and 2.
  • Example 8 The reaction and analysis were carried out in the same manner as in Example 1 except that the catalyst was changed to that prepared in Preparation Example 3 of the catalyst ( porous body made of CoF 2). The results are shown in Tables 1 and 2.
  • Example 9 The reaction and analysis were carried out in the same manner as in Example 1 except that the catalyst was changed to that prepared in Preparation Example 4 of the catalyst ( porous material made of AlF 3). The results are shown in Tables 1 and 2.
  • Example 10 The reaction and analysis were carried out in the same manner as in Example 1 except that the catalyst was changed to ⁇ -Al 2 O 3. The results are shown in Tables 1 and 2.
  • the reaction and analysis were carried out in the same manner as in Example 1 except that the ratio was 0.0: 5.6: 13.2: 79.2. The results are shown in Tables 1 and 2.
  • Example 14 Example 1 except that the gaseous reaction mixture that has passed through the first cooling collection vessel is not circulated through the stainless steel tube filled with sodium fluoride but is supplied to the second cooling collection vessel.
  • the reaction and analysis were performed in the same manner as above. The results are shown in Tables 1 and 2.
  • the reaction and analysis were carried out in the same manner as in Example 1 except that the value was 3.
  • the results are shown in Tables 1 and 2.
  • Example 16 The reaction and analysis were carried out in the same manner as in Example 1 except that the reaction temperature was 150 ° C. and the reaction pressure (pressure in the brightly quenched tube) was 0.5 MPa. The results are shown in Tables 1 and 2.
  • Example 17 The reaction and analysis were carried out in the same manner as in Example 1 except that the reaction temperature was 400 ° C. The results are shown in Tables 1 and 2.
  • Example 1 The reaction and analysis were carried out in the same manner as in Example 1 except for the points described below.
  • a catalyst pellets (mass 85 g (0.88 mol)) prepared by pressure molding NiF 2 powder were used.
  • the reaction temperature is 270 ° C.
  • the flow rate of the gas of the raw material compound supplied to the bright quenching tube was set to 1151 cm 3 / min at 0 ° C. and 101 kPa so that the gas of the raw material compound stayed in the bright quenching tube for 10 seconds. Collection by the first cooling collection container and the second cooling collection container and adsorption by the adsorbent were not performed. The results are shown in Table 1.
  • Comparative Example 1 As can be seen from Table 1, the composition of the reaction mixture discharged from the brightly quenched tube was 0.4% by volume of bromine trifluoride, 80.1% by volume of fluorine gas, and pentafluoride. Bromine was 19.5% by volume, and the reaction mixture contained a large amount of unreacted fluorine gas. Therefore, large-scale equipment is required to treat the remaining fluorine gas by recovery and abatement.
  • Example 11 From the results of Example 11, it can be seen that even under the condition that bromine gas and bromine trifluoride gas are simultaneously circulated, the conversion of the fluorine gas proceeds smoothly and bromine pentafluoride can be obtained with a purity of 99% or more. From the results of Example 12, even if the concentration of the nitrogen gas to be diluted is reduced to 55.2%, the conversion of the fluorine gas proceeds quantitatively, and bromine pentafluoride can be obtained with a purity of 99% or more. I understand.
  • Example 13 From the results of Example 13, it can be seen that when NiF 2 pellets are used as the catalyst, bromine pentafluoride can be obtained with high purity, although the conversion rate of fluorine gas is reduced. From the results of Example 14, bromine trifluoride is slightly trapped in the second cooling collection vessel unless the gaseous reaction mixture that has passed through the first cooling collection vessel is adsorbed by the adsorbent. You can see that they are gathered. From the results of Example 17, when the reaction temperature was 400 ° C., a small amount of fluorine gas remained. It is considered that this is because the decomposition reaction of bromine pentafluoride proceeded under high temperature conditions.
  • Example 20 In Example 1, 200 g of the collected material (mixture of bromine trifluoride and bromine pentafluoride) collected in the first cooling collection container was collected. Then, the bromine trifluoride was prepared by the same method as in Example 1 except that the recovered collection was used as a raw material compound, that is, the recovered collection was used as a bromine-containing compound in the vaporizer. Fluorine gas, bromine pentafluoride, and nitrogen gas are supplied to a bright quenching tube (reactor) equipped with a catalyst, and under the reaction conditions shown in Table 3 (gas composition of raw material compound and F / Br), fluorine gas and trifluoride are used. The reaction for obtaining bromine pentafluoride from bromine fluoride was continuously carried out.
  • Tables 3 and 4 show the composition of the reaction mixture obtained by the reaction and the composition of the collected material in the first cold collection container and the second cold collection container. As can be seen from Tables 3 and 4, the conversion rate of fluorine gas exceeded 99%, and bromine pentafluoride having a purity of 99% or more was collected in the second cooling collection container.

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Abstract

L'invention concerne une méthode de production de pentafluorure de brome, par laquelle il devient possible de réduire la quantité d'un gaz fluoré n'ayant pas réagi restant et de produire du pentafluorure de brome ayant une pureté élevée. La méthode de production de pentafluorure de brome comprend : une étape de réaction consistant à acheminer un composé contenant du brome qui est au moins un composé parmi un gaz de brome et du trifluorure de brome et un gaz fluoré dans un réacteur (1), de telle sorte que le rapport molaire F/Br des atomes de fluor aux atomes de brome peut devenir de 3,0 à 4,7 inclus pour effectuer une réaction du composé contenant du brome avec le gaz fluoré, ce qui permet de produire un mélange réactionnel comprenant du pentafluorure de brome et du trifluorure de brome ; et une étape de séparation consistant à séparer le pentafluorure de brome et le trifluorure de brome l'un de l'autre dans le mélange réactionnel.
PCT/JP2020/034334 2019-10-07 2020-09-10 Méthode de production de pentafluorure de brome WO2021070550A1 (fr)

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